Structure determination of KScS2, RbScS2 and KLnS2 (Ln = Nd,Sm, Tb,Dy, Ho,Er, Tm and Yb) and crystal–chemical discussion

The title structures of KScS₂ (potassium scandium sulfide), RbScS₂ (rubidium scandium sulfide) and KLnS₂ [Ln = Nd (potassium neodymium sufide), Sm (potassium samarium sulfide), Tb (potassium terbium sulfide), Dy (potassium dysprosium sulfide), Ho (potassium holmium sulfide), Er (potassium erbium sulfide), Tm (potassium thulium sulfide) and Yb (potassium ytterbium sulfide)] are either newly determined (KScS₂, RbScS₂ and KTbS₂) or redetermined. All of them belong to the α‐NaFeO₂ structure type in agreement with the ratio of the ionic radii r³⁺/r⁺. KScS₂, the member of this structural family with the smallest trivalent cation, is an extreme representative of these structures with rare earth trivalent cations. The title structures are compared with isostructural alkali rare earth sulfides in plots showing the dependence of several relevant parameters on the trivalent cation crystal radius; the parameters thus compared are c, a and c/a, the thicknesses of the S—S layers which contain the respective constituent cations, the sulfur fractional coordinates z(S²⁻) and the bond‐valence sums.     

Infra-red free-carrier absorption due to impurity scattering in semiconducting quantum well structures

The theory of free-carrier absorption (FCA) is developed, in the extreme quantum limit when the carriers are assumed to populate only the lowest quantized energy level, for quasi-two and one-dimensional semiconducting quantum well structures where the carriers are scattered by ionized impurities. The radiation field is assumed to be polarized in the plane of the layer in the quasi-two-dimensional case and along the length of the wire in the quasi-one-dimensional case. Expressions for FCA are obtained for the cases where the impurities are either in the well (background impurities) or outside the well (remote impurities). Variation of FCA is numerically studied with photon frequency and well width.     

极谱法测定硫酸稀土复盐母液中的稀土总量

在pH9.0的NH3·H2O-(NH4)2SO4缓冲介质中,RE(Ⅲ)-TP的络合吸附波的波高与RE(Ⅲ)的浓度在0-10μg/mL间成线性。该方法的相对标准偏差2.23%,回收率99.51%-103.38%,用于硫酸稀土复盐母液中微量稀土总量测定,结果满意。     

稀土甘氨酸咪唑配合物[RE(Gly)4(Im)(H2O)](ClO4)3的热化学研究

采用溶解-反应量热法在具有恒温环境的溶解-反应热量计内,测定了[Gd(Gly)4(Im)(H2O)](ClO4)3和[Y(Gly)4(Im)(H2O)](ClO4)3两种稀土甘氨酸咪唑配合物的标准生成焓分别为(-3 461.46 ±0.22) kJ·mol-1 和(-3 926.6±0.90) kJ·mol-1.     

The spectrum of Nd in rare earth orthoaluminates. The trigonal to orthorhombic transition study of the level

Some structural and spectroscopic features of rare earth orthoaluminates are examined.The trigonal→ orthorhombic transition is studied in a series of Nd_xSm_1−xAlO₃ compounds. The evolution of the crystal structure is followed by X-ray analysis and optical absorption. The free ion and crystal field parameters of Nd³⁺ (4f³ configuration) are determined in LuAlO₃:Nd³⁺.The anomaly of the calculated splitting of the levels is slight, but well characterized in NdAlO₃. The spin correlated crystal field and orbitally correlated crystal field models are tested as well as an empirical correction which was proposed earlier.     

Luminescence and lifetime characteristics of microphases in KCl:KI:Pb mixed crystals

Absorption and luminiscence measurements were performed on lead-doped KCl:KI mixed single crystals. Strong differences were found between as-grown and quenched samples. New bands were observed in the absorption spectra of unquenched samples in the spectral region between the limit positions of the A bands, corresponding to chloride or iodide lattices. The strong band at 449 nm dominates the luminescence of these samples at low temperatures. Its kinetics have a complicated form and the decay time is in the interval from ns to ms. Quenched samples have a well-known luminescence spectrum caused by octahedral lead impurity centres in KCl single crystals. The kinetics, however, also indicate mixed chlorine and iodine coordination of lead in the investigated crystals.     

稀土粉末Eu∶Y_2O_3的自由感应衰减量子拍

稀土固体是重要的激光和光电子材料。目前 ,由于以宽带信号和太赫兹比特数据传输率为特征的信息技术的发展 ,稀土固体材料的相干瞬态动力学过程成为宽带与高速信息光子学的基本物理问题之一。研究了室温下稀土粉末样品Eu3+ ∶Y2 O3自由感应衰减的相干瞬态光谱 ,这有助于理解有效的光吸收动力学、激发态弛豫、相干能量传递和超短光脉冲在稀土固体中的传播。用一对紫外飞秒相干光脉冲作用于稀土粉末样品Eu3+ ∶Y2 O3,然后监测物质激发态的布居数随两个激发脉冲之间的延时的变化 ,测量到其自由感应衰减量子拍 (FID) ,从拍频周期分析确定了其能级精细结构 ,能级的退相时间长达皮秒量级。理论分析和实验结果符合得很好。对稀土离子的量子干涉的研究 ,表明其在受激受控光放大方面具有潜在的应用前景     

Influence of isovalent substitutions on absorption spectra of orthoferrities

The role of impurity ions in formation of the optical properties of rare-earth orthoferrites is investigated. Optical spectra of the substituted against unsubstituted orthoferrites are presented. The influence of different isovalent substitutions on the optical absorption of orthoferrites that are promising for magnetooptics is studied. Institute of Solid-State and Semiconductor Physics of the Academy of Sciences of Belarus, 17, P. Brovka St., Minsk, 220072, Belarus. Translated from zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 642–645, September–October, 1997.     

碱土金属氟卤化物中的Eu3+的荧光光谱特征

本文系统研究了MFX体系中Eu³⁺荧光光谱特征,着重讨论了X^-,M²⁺及杂质缺陷(主要为O^2-)对Eu³⁺发光的影响.     

Solid phase extraction for analysis of biogenic carbonates by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS): an investigation of rare earth element signatures in otolith microchemistry

Uptake of trace elements into fish otoliths is governed by several factors such as life histories and environment in addition to stock and species differences. In an attempt to elucidate the elemental signatures of rare earth elements (REEs) in otoliths, a solid phase extraction (SPE) protocol was used in combination with electrothermal vaporization (ETV) as a sample introduction procedure for the determinations by inductively coupled plasma quadrupole mass spectrometry (ICP-MS). Effects of various parameters, such as carrier gas flow rate, atomization temperature and chemical modification, were examined for optimization of the conditions by ETV-ICP-MS. Atomization was achieved at 2800 °C. Lower temperatures (i.e. 2600 °C) resulted in severe memory problems due to incomplete atomization. Palladium was used as a chemical modifier. It was found that an increase in Pd concentration up to 0.5 μg in the injection volume (70 μl) led up to four-fold enhancement in the integrated signals. This phenomenon is attributed to the carrier effect of Pd rather than the stabilization since no significant losses were observed for high temperature drying around 700 °C even in the absence of Pd. Preconcentration was performed on-line at pH 5 by using a mini-column of Toyopearl AF-Chelate 650M chelating resin, which also eliminated the calcium matrix of otolith solutions. After preconcentration of 6.4 ml of solution, the concentrate was collected in 0.65 ml of 0.5% (v/v) HNO₃ in autosampler cups, and then analyzed by ETV-ICP-MS. The method was validated with the analysis of a fish otolith certified reference material (CRM) of emperor snapper, and then applied to samples. Results obtained from otoliths of fish captured in the same habitat indicated that otolith rare earth element concentrations are more dependent on environmental conditions of the habitat than on species differences.